EP1165678A1 - Utilisation d'esters d'alcanolamine d'acide gras - Google Patents

Utilisation d'esters d'alcanolamine d'acide gras

Info

Publication number
EP1165678A1
EP1165678A1 EP00904944A EP00904944A EP1165678A1 EP 1165678 A1 EP1165678 A1 EP 1165678A1 EP 00904944 A EP00904944 A EP 00904944A EP 00904944 A EP00904944 A EP 00904944A EP 1165678 A1 EP1165678 A1 EP 1165678A1
Authority
EP
European Patent Office
Prior art keywords
acid
esters
fatty acid
carbon atoms
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00904944A
Other languages
German (de)
English (en)
Other versions
EP1165678B1 (fr
Inventor
Sergio Milan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1165678A1 publication Critical patent/EP1165678A1/fr
Application granted granted Critical
Publication of EP1165678B1 publication Critical patent/EP1165678B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the invention is in the field of thermoplastics and relates to the use of selected nitrogenous surfactants as antistatic additives.
  • Thermoplastic materials preferably PVC
  • PVC polyvinyl ethylene
  • Thermoplastics like most plastics, are pronounced insulators due to their chemical constitution.
  • a disadvantage is that the substances charge electrostatically very easily and once applied, charges cannot be removed quickly enough due to the low surface conductivity. In practice, the electrostatic charging of plastics can both cause annoyance and create serious dangerous situations. The main ones are:
  • antistatic agents are usually added to the thermoplastics, which make it easier to discharge the charges from the surface.
  • examples of internal antistatic agents, ie substances that are added to the polymer mass before or during processing, are anionic, nonionic or cationic surfactants. An overview of this can be found in S.Riethmayer in Gummi, Asbest, Kunststoffst., 26, p.76-88 , 182-184, 298-308, 419-429, 507-512 (1973).
  • Antistatic agents for PVC which are mixtures of complex esters, alkylbenzenesulfonates and alkyl sulfates, are known from the Japanese patent application with the application number JP-94/226266 (Henkel). From the German patent application (Henkel) DE-A1 4304468 polyol complex esters are known for the same application. Finally, as a commercial product with the designation "Dehydat 80-X" are antistatic agents for the PVC finishing of the company Henkel known, the mixtures of anionic surfactants (secondary alkanesulfonates) and nonionic surfactants (amine polyglycol ether).
  • the object of the present invention was to equip thermoplastics in general and polyvinyl chloride and polyolefins in particular in such a way that on the one hand the electrostatic charge is significantly reduced and on the other hand transparent and permanently protected films are obtained.
  • the invention relates to the use of fatty acid alkanolamine esters as antistatic agents for thermoplastics, especially for polyvinyl chloride and polyolefins.
  • fatty acid alkanolamine esters not only impart excellent antistatic properties to thermoplastic plastics, but also lead to transparent films which, even after prolonged storage, show hardly any tendency towards clouding.
  • the antistatic upgrade can generally relate to thermoplastics.
  • thermoplastics such as polyolefins, such as low density and high density polyethylene, polypropylene, polystyrene, vinyl polymers, polyamides, polyesters, polyacetals, polycarbonates and polyurethanes.
  • polyvinyl chlorides are preferably added, which in particular have K values in the range from 30 to 80.
  • Fatty acid alkanolamine esters are preferably added, which in particular have K values in the range from 30 to 80.
  • fatty acid alkanolamine esters are known substances.
  • fatty acid triethanolamine esters are used as antistatic agents, which preferably follow the formula (I)
  • Typical examples of fatty acid triethanolamine esters which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
  • Ci6 / 18 coconut fatty acids and in particular partially hardened Ci6 / 18 tallow or palm fatty acids and high-elicinate Ci6 / ß ⁇ fatty acid cuts are preferably used.
  • the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the esters.
  • an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred fatty acid triethanolamine esters are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical Ci6 / 18-Taig or palm fatty acid (iodine number 0 to 40). From an application point of view, fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO is an acyl radical having 16 to 18 carbon atoms, R 2 is R 1 CO, R 3 is hydrogen and m, n and p are 0 .
  • esters of fatty acids with diethanolalkylamines of the formula (II) are also suitable as antistatic agents.
  • R 1 CO for an acyl radical with 6 to 22 carbon atoms
  • R 2 for hydrogen or R 1 CO
  • R 4 for an alkyl radical with 1 to 4 carbon atoms
  • m and n in total for 0 or numbers of 1 to 12.
  • suitable trialkanolamine esters are the esters of fatty acids with 1,2-dihydroxypropyldialkylamines of the formula (III)
  • R CO stands for an acyl radical with 6 to 22 carbon atoms
  • R 2 for hydrogen or R 1 CO
  • R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms and m and n in total for 0 or numbers from 1 to 12 stands.
  • the examples given for (I) also apply to the alkanolamine esters of the formulas (II) and (III).
  • the fatty acid alkanolamine esters are used together with lubricants of the partial glyceride type, which bring about a synergistic improvement in color stability.
  • Partial glycerides ie monoglycerides, diglycerides and their technical mixtures, can still contain small amounts of triglycerides due to the production process.
  • the partial glycerides preferably follow the formula (IV)
  • R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 7 and R 8 independently of one another for R 6 CO or OH and the sum (m + n + p ) stands for 0 or numbers from 1 to 100, preferably 5 to 25, with the proviso that at least one of the two radicals R 7 and R 8 is OH.
  • Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid, linoleic acid Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • Technical lauric acid glycerides, palmitic acid glycerides, stearic acid glycerides, isostearic acid glycerides, oleic acid glycerides, behenic acid glycerides and / or erucic acid glycerides are preferably used, which have a monoglyceride content in the range from 50 to 95. preferably have 60 to 90 wt .-%.
  • the weight ratio between the trialkanolamine esters and the partial glycerides can vary in the range from 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60.
  • the fatty acid alkanolamine esters are used together with lubricants of the sorbitan ester type, which likewise bring about a synergistic improvement in color stability.
  • Sorbitan esters preferably follow the formula (V),
  • R 9 CO represents linear or branched, saturated or unsaturated acyl radicals having 6 to 22 and preferably 12 to 18 carbon atoms.
  • formula (I) only represents sorbitan monoesters, sorbitan di, sesqui and triesters and mixtures thereof are also considered.
  • Typical examples are mono-, sesqui-, di- and / or triester of sorbitan with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, petroselinic acid Linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • Sorbitan monopalmitate and sorbitan monostearate are particularly preferred.
  • the weight ratio between the trialkanolamine esters and the sorbitan esters can vary in the range from 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60.
  • the powdered or granulated polymers are mixed with the additives and homogenized intensively.
  • the additives for example flow improvers, stabilizers, lubricants, antistatic agents, plasticizers etc.
  • masterbatch ie a homogeneous mixture of all additives and then to mix them with the plastic.
  • masterbatch ie a homogeneous mixture of all additives and then to mix them with the plastic.
  • the additive mixture ie for example by extrusion, injection molding, calendering, rolling, blow molding, stretch drawing and the like.
  • the fatty acid alkanolamine esters can also be used as external antistatic agents, ie the esters are applied to the surface from an aqueous or alcoholic solution.
  • the fatty acid alkanolamine esters can be used together with other auxiliaries and additives for the production and processing of thermoplastics, such as, for example, flow and impact resistance improvers, lubricants, stabilizers, plasticizers, co-antistatics, fillers, color pigments and the like.
  • Suitable impact modifiers are ethylene-vinyl acetate copolymers as the graft base, ethylene-vinyl acetate / vinyl chloride graft polymers,
  • Graft polymers chlorinated polyethylene, methyl methacrylate-butadiene-styrene graft polymer and acrylonitrile-butadiene-styrene terpolymer (the latter two for indoor use).
  • Typical lubricants include, for example, hydrocarbons (paraffin oils, natural paraffins, synthetic paraffins, low and high density polyethylene waxes, polypropylene waxes), alcohols (cetyl alcohol, stearyl alcohol, tallow fatty alcohol), ketones (stearone), carboxylic acids (lauric acid, myristic acid, palmitic acid, stearic acid, stearic acid , tallow fatty acid, arachidic acid, behenic acid, montanic acid, oxidized polyethylene waxes), metal salts of carboxylic acids (calcium stearate, zinc stearate, lead stearate, calcium montanate, calcium salts of oxidized polyethylene waxes or synthetic wax acids), carboxylic acid (oleic acid amide, erucic acid amide, stearic acid amide, ethylene di-stearoyldiamid) Carbonklareester (Ethyl stearate, n-butyl stea
  • Glycerol tribehenate glycerol trimontanate, pentaerythritol tetrastearate, pentaerythritol tetra-behenate, mixed esters of adipic acid, pentaerythritol and stearic acid, montanic acid esters, partially saponified montanic acid esters).
  • the esterquats are used together with lubricants of the fatty acid, fatty alcohol and / or partial glyceride type used, the weight ratio of the components can be in the range from 90:10 to 60:40.
  • the mixtures have the advantage that they have a very positive influence on the color stability of the plastics.
  • the stabilizers are divided into UV adsorbers (hydroxybenzophenones, hydroxyphenylbenzotriazoles, cinnamic acid esters, oxalanilides), quenchers (essentially nickel complexes), hydroperoxide decomposers (thiocarbamates, thiophosphates, thiobisphenolates) and radical scavengers (sterically hindered amines).
  • UV adsorbers hydroxybenzophenones, hydroxyphenylbenzotriazoles, cinnamic acid esters, oxalanilides
  • quenchers essentially nickel complexes
  • hydroperoxide decomposers thiocarbamates, thiophosphates, thiobisphenolates
  • radical scavengers sterically hindered amines
  • ⁇ -keto compounds such as, for example, ⁇ -diketones or ⁇ -keto carboxylic acids are also suitable.
  • plasticizers examples include phthalic acid esters (dimethyl phthalate, diethyl phthalate, di-butyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-i-octyl phthalate, di-i-nonyl phthalate, di-i-decyl phthalate, di -i-tridecylphthalate, dicyclohexalphthalate,
  • Carbonates (calcium carbonate, dolomite), silicates (talc, asbestos, kaolin, mica), silicon dioxide, aluminum hydroxide, carbon black, organic substances (nutshells, wood flour, corn cobs), glass fibers, glass balls, hollow glass balls, carbon fibers, aramid fibers, whiskers and the like come as fillers in question.
  • suitable color pigments are titanium dioxide, iron oxides, carbon black, chrome yellow pigments, molybdate red pigments, chromium oxide green pigments, mixed phase pigments and cadmium pigments.
  • the amount of auxiliaries added can be 1 to 10 and preferably 4 to 8 parts by weight, based on 100 parts by weight of thermoplastic.
  • Dehyquart AU 46 based on partially hardened tallow fatty acid **) Dehyquart AU 18: based on stearic acid
  • Dehyquart F30 Mixture of (a) 30 parts of ester quat base partially hardened palm fatty acid and (b) 70 parts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'esters d'alcanolamine d'acide gras comme antistatiques pour des matières thermoplastiques, notamment pour des chlorures de polyvinyle et des polyoléfines.
EP00904944A 1999-01-30 2000-01-22 Utilisation d'esters d'alcanolamine d'acide gras Expired - Lifetime EP1165678B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19903715 1999-01-30
DE19903715A DE19903715C2 (de) 1999-01-30 1999-01-30 Verwendung von Fettsäurealkanolaminestern als interne Antistatika für thermoplastische Kunststoffe
PCT/EP2000/000467 WO2000044824A1 (fr) 1999-01-30 2000-01-22 Utilisation d'esters d'alcanolamine d'acide gras

Publications (2)

Publication Number Publication Date
EP1165678A1 true EP1165678A1 (fr) 2002-01-02
EP1165678B1 EP1165678B1 (fr) 2006-05-03

Family

ID=7895893

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00904944A Expired - Lifetime EP1165678B1 (fr) 1999-01-30 2000-01-22 Utilisation d'esters d'alcanolamine d'acide gras

Country Status (6)

Country Link
US (1) US6835765B1 (fr)
EP (1) EP1165678B1 (fr)
DE (2) DE19903715C2 (fr)
ES (1) ES2262505T3 (fr)
PT (1) PT1165678E (fr)
WO (1) WO2000044824A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2404662A (en) * 2003-08-01 2005-02-09 Reckitt Benckiser Cleaning composition
DK1908583T3 (en) * 2005-07-28 2015-11-09 Jfe Steel Corp The resin-coated metal sheet
US9018288B2 (en) * 2007-08-02 2015-04-28 Lubrizol Advanced Materials, Inc. Thermoplastic composition
EP2607418A1 (fr) * 2011-12-21 2013-06-26 LANXESS Deutschland GmbH Combinaisons d'agents de démoulage

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE507814A (fr) * 1950-12-22
GB867176A (en) * 1959-12-02 1961-05-03 Petrochemicals Ltd Improvements in or relating to thermoplastic polymeric compositions
DE2005854B2 (de) 1970-02-10 1973-04-12 Chemische Werke Hüls AG, 4370 Mari Antielektrostatische thermoplastiche formmassen zur herstellung von formkoerpern
JPS555934A (en) * 1978-06-26 1980-01-17 Polyplastics Co Polyacetal resin composition
DE4243550C1 (de) 1992-12-22 1994-06-01 Henkel Kgaa Faserhilfsmittel und deren Verwendung
JPH06226266A (ja) 1993-02-02 1994-08-16 Akiyoshi Ajisawa 六価クロムの除去方法
DE4304468A1 (de) 1993-02-15 1994-08-18 Henkel Kgaa Verfahren zur Herstellung hellfarbiger Polyolester
DE19526742C2 (de) * 1994-08-12 1997-09-18 Vinnolit Kunststoff Gmbh Antistatikadditiv, Verfahren zu dessen Herstellung sowie dessen Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0044824A1 *

Also Published As

Publication number Publication date
DE19903715A1 (de) 2000-08-10
WO2000044824A1 (fr) 2000-08-03
PT1165678E (pt) 2006-07-31
ES2262505T3 (es) 2006-12-01
DE19903715C2 (de) 2002-12-05
EP1165678B1 (fr) 2006-05-03
US6835765B1 (en) 2004-12-28
DE50012694D1 (de) 2006-06-08

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